Primary xenoxy-alkyl amines



Patented Jan. 1940 UNITED. STATES 1Pmlarrrv OFFICE Francis N. Alquist and Harold R. Slagh,,Midland, Mich., assignors to The Dow Chemical Company, Midland, Mich, a. corporation of Michigain 'No Drawing. Application July 27, 1938,

Serial No.'221,606

6 Claims. (Cl. 260-571) This invention concerns a group of novel priand the reacted charge dispersed in an excess of mary amines, a method for their preparation, Water. The water dispersion was extracted with "and the hydrochlorides preparable therefrom. benzene, and the benzene extract dried and frac- The new compounds falling within the scope of tionally distilled, whereby there was obtained f5 this invention have the formula ROR'-NH2 0.125 mol of beta-Z-xenoxy-ethyl amine as a 5 wherein R'representsax'enyl radical and R repcolorless liquid boiling at 190 to 194 C. at 0.7 resents a lower alkylene group, and the hydroinch pressure, and having the specific gravity chlorides thereof. 1.106 at 25/25 C. This compound has a char- Our new primary amines are prepared by reacteristic amine odor and the formula 10 acting'a xenoxy-alkyl halide with an excess of I 10 liquid ammonia. The reaction is carried out by G heating a mixture of the reactants in the liquid I *CaHa-NH:

phase at temperatures preferably betweeen 125 H o v C. and the decomposition temperature of the re- A portion of the beta-Z-xenoxy-ethyl amine, as

action mixture, although somewhat lower temobtained above,'was dissolved in benzene and dry 15 .peratures may be employed. The reaction preshydrogen chloride bubbled through the solution sure is autogenous. When the reaction is comto precipitate therefrom a solid hydrochloride plete, the ammonia is distilled ofi and the reaction salt. This precipitate was separated by filtration mixture diluted with water or aqueous alkali, and and dried to obtain beta-2-xenoxy-ethy1 amine thereafter extracted'with benzene. The benzene hydrochloride as white, shining crystals melting 20 extract is dried and fractionally distilled to obtain at 191 C. This compound is relatively waterthe desired primary amine compound. soluble.

The hydrochlorides of these primary amine In a similar manner, other xenoxy-alkyl compounds may be readily prepared by dissolving halides, such as the bromides and iodides, may the amine in a suitable organic solvent, e. g., be reacted with liquid ammonia to form primary 5 benzene or petroleum ether, and thereafter amine compounds falling within the scope of this bubbling dry hydrogen chloride through the soluinvention. Representative of the xenoxy-alkyl tion to precipitate the desired amine salts. These halides which may be so reacted are beta-2- hydrochlorides are generally'solid, crystalline xenoxy-ethyl bromide, a white, crystalline solid 80 compounds and soluble in water. melting at 665 C. and boiling at 170 to 175 c.

The expressions xenyl, xenoxy, and zenol, at .5 millimeters pressure; beta-l-xenoxy-ethyl as herein employed, refer to diphenyl and phenylchloride, a crystalline compound melting at 130 phenoxy radicals and to the phenylphenols, re- 0- and boi i g at 163-165 C. at 3 millimeters spectively, and include such radicals and compressure; (b ahyl)-(gamma-2-xenoxy) -n- 86 pounds wherein the benzene nuclei may be subpropyl chloride, an oil boiling at 170 to 173 C. stituted by alkyl or halogen. at 5 millimeters pressure; beta-2-(5-chloro- The xenoxy-alkyl halides employed as reactants xenoxy)-ethyl chloride, a viscous oil boiling at in the preparation of our new amine compounds 149 to 150 C. at 3 millimeters pressure; beta-2- may be prepared by the reaction of an alkylene (5-isopmpy1-Xe Xy) ethy1 chloride, an oil boil- '40 dihalide with an alkali metal xenolate, e. g., song at 1 0 to 153 C. at 2 millimeters pressure, 40 dium-ortho-phenyl phenolate. The xenoxyand having a specific gravity of 1.093 at 20 0.,

alkyl halides are all high-boiling compounds and etc. Other similar compounds which may be emvary in characteristic from viscous oils to highployed are omega-2-xenoxy-n-amyl chloride. melting solids. gamma-Z- (5-bromo-xenoxy) -propyl bromide, be-

The following example is illustrative of one way ta-Z-(5 tertiary-butyl-xenoxy) ethyl chloride, 45 in which our new method may be applied and of beta-2-xenoxy-ethyl iodide, beta-4- 2.6-dimeththe compounds obtained thereby, but is not to be y -X n0Xy)- y1 chloride. and the like. The construed as limiting the invention: hydrochlorides of the primary amines obtained Example by the reaction of the above xenoxy-alkyl halides and ammonia may be readily prepared substan- 0.25 mol of beta-2-xenoxyethyl chloride and 5 tially as described in the foregoing example. mols of liquid ammonia were charged into a stain- The amine compounds falling within the scope less steel bomb and heated with agitation at 150 of the present invention are of value as corrosion C. for 3 hours. The bomb was then cooled to room inhibitors in acid solutions. For example, a 1 per temperature, the unreacted ammonia separated, cent solution of beta-Z-xenoxy-ethyl amine in 5 10.09 per cent hydrochloric acid was prepared. Weighed iron strips of 6.75 square inches surface area were suspended in this solution and in a control solution of 10.09 per cent hydrochloric acid to determine the inhibiting effect of the amine. After 16 hours at room temperature the test specimens suspended in the control solution were found to have lost 0.798 and 0.727 gram in weight, respectively. Similar metallic strips suspended in the hydrochloric acid-amine solution showed a weight loss of only 0.037 and 0.047 gram, respectively, after 16 hours. The presence of the amine fraction in aqueous acid solution, therefore, accounted for a reduction in excess of 93 per cent of the total weight lost by corrosion.

We claim:

1. A compound selected from the group consisting of (1) primary amines having the formula R-O-RNH2 wherein R represents a xenyl radical and R, represents a lower alkylene group, and (2) the hydrochlorides thereof.

2. A primary amine having the formula R-O-R'--NH2 wherein R represents a xenyl radical and R represents a lower alkylene group.

3. An amine hydrochloride having the formula (R-O-R-NH2) 'HCl wherein R represents a xenyl radical and R represents a lower alkylene group.

4. A primary amine having the formula wherein R represents a lower alkylene group.

5. Beta-2-xen0xy-ethyl amine having the for- 5. A method comprising the steps of reacting a xenoxy-alkyl halide with an excess of liquid ammonia at a temperature between about C. and the decomposition temperature of the reaction mixture and under autogenous pressure, and thereafter separating from the reaction mixture a primary amine compound having the formula R-OR-NH2 wherein R represents a xenyl radical and R represents a lower alkylene group.

FRANCIS N. ALQUIST.

HAROLD R. SLAGH. 

